EP1136509B1 - Durcisseurs de résines époxydes, procédé pour leur préparation et utilisation - Google Patents

Durcisseurs de résines époxydes, procédé pour leur préparation et utilisation Download PDF

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Publication number
EP1136509B1
EP1136509B1 EP01106910A EP01106910A EP1136509B1 EP 1136509 B1 EP1136509 B1 EP 1136509B1 EP 01106910 A EP01106910 A EP 01106910A EP 01106910 A EP01106910 A EP 01106910A EP 1136509 B1 EP1136509 B1 EP 1136509B1
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Prior art keywords
amine
reaction
epoxide
compounds
polyamines
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German (de)
English (en)
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EP1136509A1 (fr
Inventor
Markus Dr. Schrötz
Martin Fulgraff
Peter Martischewski
Jürgen Dr. Schillgalies
Rolf Dr. Herzog
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Hexion GmbH
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Bakelite AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins

Definitions

  • the invention relates to hardeners for epoxy compounds which are emulsifiable in water and / or are soluble and preferred for the preparation of aqueous epoxy resin emulsions or find dispersions use.
  • EP-B 0 387 418 discloses water-emulsifiable curing agents for epoxy resins which are disclosed in US Pat good properties profile of the cured products a low viscosity, a light color and have a good emulsifying effect.
  • curing agents are prepared by reaction of polyalkylene polyether monoamines and / or diamines and / or polyamines with a average molecular weight of 148-5000, with di- and / or polyepoxide compounds, optionally after reaction or in admixture with monoepoxide compounds, reaction of the epoxide group-containing precursor thus obtained with a primary or secondary Mono- and / or di- and / or polyamine, wherein the secondary amine is at least two has secondary amino groups and the amine or amine mixture used in such Amount is used that the epoxy groups capable of reaction to the nitrogen located hydrogen atoms in a ratio of 1: 2 to 1: 10.
  • This pot life indicator is to be understood as follows: One applied to a substrate aqueous emulsion dries. This breaks the emulsion and the remaining droplets of the non-aqueous phase, ideally resin and hardener in the correct mixing ratio included, film before the film then hardens chemically. The length of time from creating the emulsion until the time when from the emulsion no more films or in their Properties deficient films can be formed, is the pot life. This pot life may be much shorter than the processing time, i.e., the time in which the emulsion can be applied to a substrate. It is therefore advantageous if a Binder system indicates the end of the pot life by already at the end of the pot life the Viscosity of the emulsion increases so much that processing is no longer possible.
  • Water-emulsifiable hardeners for epoxy resins having a pot-life display are EP-A 0 821 021 known. These are reaction products of aliphatic polyols with Epoxy resins, which are then reacted with polyamines. The reaction of polyols with resins runs off only at greatly elevated temperature under catalysis. This is caused by Homopolymerization of the Resin Products with increased viscosity and the resin must be in be used in large excess. This deteriorates the emulsifiability of correspondingly prepared adducts.
  • curing agent according to claims 1 to 6 and by Process for their preparation according to claims 7 to 11.
  • These curing agents are suitable in particular together with one or more epoxy compounds and water and optionally fillers and additives such as e.g. Pigments, defoamers or deaerators, for the production of paints, coatings and coatings, as well as additives for hydraulic binders.
  • these curing agents are particularly suitable together with one or more epoxy compounds and optionally fillers and additives such as e.g. Pigments, defoamers or deaerators for the production of sealants and adhesives and of flexible molded parts, fabrics and laminates and find for these Use according to claims 12 to 15.
  • this product is not suitable alone as a curing agent for water-emulsifiable epoxy resin systems, because it forms due to the high content of alkylene oxide, coatings whose water resistance does not meet the quality requirements. In addition, for the same reason, the cure is delayed too much and the films show too low final strengths.
  • component a still contain the following components: amine-terminated adduct of an epoxy resin and an amine as characterized in claim 1 and the adduct is substantially free of unreacted Amines (component b) and amine-terminated adduct of a reactive diluent and a primary or secondary mono- and / or di- and / or polyamine, wherein the secondary amine has at least two secondary amino groups and the adduct is substantially free of unreacted amines (US Pat. Component c).
  • component b amine-terminated adduct of an epoxy resin and an amine as characterized in claim 1 and the adduct is substantially free of unreacted Amines
  • component c amine-terminated adduct of a reactive diluent and a primary or secondary mono- and / or di- and / or polyamine, wherein the secondary amine has at least two secondary amino groups and the adduct is substantially free of unreacted amines
  • Adducts hardener obtained with a significantly improved property spectrum: There are in their aqueous emulsion with epoxy liquid resins alkali-resistant hardener, with a low viscosity, a light intrinsic color and low toxic potential, which do not tend to carbamate, which can be easily emulsified in water, with construction site-appropriate tools and in admixture with the corresponding stoichiometric amounts of epoxy resins and optionally reactive diluents and water, preferably at a water content of 40-60%, based on the organic substance, even at low temperatures cure rapidly, the corresponding emulsions have a clearly recognizable pot-life end and the cured coatings waterproof, shiny and yellowing.
  • the curing agents show a very high reactivity with correspondingly short pot life. she are therefore only suitable for use in machine processing processes where short Processing times are allowed or even desired. For manual processing The reactivity of the curing agent must be reduced accordingly. This is achieved in that the curing agents are still used with up to 50 mol%, based on the amino groups, Reactive thinners are implemented.
  • reaction with the di- and / or polyepoxide which also optionally after Reaction or blending with monoepoxides can be done with the EP-B 0 387 418 known methods carried out - usually by implementation of Reactants with each other at temperatures in the range of 20-120 ° C, preferably in Range of 50 - 90 ° C and keep the reaction mixture for about 1-5 h at a Temperature in this area. Subsequently, a distillative separation of the in the 2nd Reaction step unreacted amines.
  • the quantitative ratio of the sum of the polyalkylene ether amines to the di- and / or Polyepoxide compounds is chosen so that the resulting products at least one free Epoxide group per molecule, d. H. the amount of epoxide compounds with more than one epoxide group per molecule is chosen so that the ratio of, optionally after the reaction with monoepoxide compounds remaining bound to nitrogen Hydrogen atoms capable of reacting with epoxide groups to the epoxide groups of di- or polyepoxide compounds in the range of 1: 1.4 to 6.
  • polyalkylene polyether monoamines and / or diamines and / or polyamines are used as the amine component for this first reaction step.
  • These polyalkylenepolyetheramines have average molecular weights of 148 to 5000, preferably between 400 and 2000.
  • the quantitative ratio of the polyethylenepolyetheramines to the polypropylenepolyetheramines ranges from 5:95 to 95: 5. Up to 10% of polybutylenepolyetheramines can be added thereto.
  • polyethylenepolyetheramines are more hydrophilic than polypropylenepolyetheramines and polybutylenepolyetheramines, it is possible, by a specific combination with a suitable mixing ratio of the various polyalkylenepolyetheramines, to obtain the HLB value of the curing agent obtained after mixing components a, b and c and optionally further in reaction with preferably monofunctional epoxide compounds to be adjusted so that at different proportions of the individual components over wide ranges an optimum in terms of emulsifiability and water resistance of the cured coating is achieved.
  • epoxy components for the first reaction step and for the preparation of Component b are predominantly epoxy compounds with more than one epoxide group each Molecule.
  • epoxy compounds with only one epoxide group per molecular unit become.
  • Examples of these are butyl, hexyl, phenyl, butylphenyl or Kresylglycidylether.
  • mono-glycidyl compounds such as glycidyl esters, amines, -thioethers, -amides, - (iso) cyanates, aralkylene oxides and glycidylated fatty alcohols.
  • the epoxides polyunsaturated Hydrocarbons (vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, Cyclododecatriene, isoprene, 1,5-hexadiene, butadiene, polybutadienes, divinylbenzenes and the like), oligomers of epichlorohydrin and the like, epoxide ethers of polyhydric alcohols (Ethylene, propylene and butylene glycols, polyglycols, thiodiglycols, glycerol, Trimethylolpropane, pentaerythritol, sorbitol, polyvinyl alcohol, polyallylalcohol and the like), Epoxide ethers of polyhydric phenols (re
  • Preferred epoxide compounds are liquid and solid polyphenol glycidyl ethers at room temperature, z.
  • Such epoxy resins have an epoxide equivalent of 160-> 700.
  • the above polyfunctional epoxy compounds also includes the Term epoxy resin, may individually or in a mixture, optionally in the presence of Solvents are reacted according to the present method. You can also, like already mentioned above, be used in mixtures with monoepoxides.
  • the amine components used for the second reaction step and for the preparation of components b and c are: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-, 1,3- and 1,4 Diaminobutane, 3- (2-aminoethyl) aminopropylamine, N, N'-bis (3-aminopropyl) ethylenediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, N-aminoethylpiperazine, N-aminopropylpiperazine , N-aminobutylpiperazine, phenylenediamines, xylylenediamines and isophoronediamine, or mixtures of these amines.
  • the amount of amine or amine mixture to be used should be such that it is used at least in a 10% molar excess, based on the epoxide groups of the precursor. This excess can be unlimited due to chemical considerations. But since the excess amines must be distilled off again, it is necessary for economic reasons to limit the surplus. In general, the amines are therefore used in a 10 to 100% molar excess, based on the epoxide groups of the precursor.
  • the second reaction step is carried out in such a way that the product from the 1st reaction step mixed directly with the selected amine or amine mixture and at a temperature in the Range of 20-120 ° C, especially in the range of 50-90 ° C, for several hours (1-5 h) is treated. This is followed by a distillative separation of the free, not transesterified Amines, preferably under vacuum.
  • an epoxy resin can all The above-mentioned epoxy compounds having more than one epoxy group per molecule and as Amine component all the above amines can be used, which can be distilled without decomposition. Again, the amines at least in a 10% molar excess, based on the epoxide groups of used epoxy resins used. This excess may be due to chemical considerations to be unlimited. But since the excess amines must be distilled off again, is off economic reasons, to limit the surplus. In general, the Amines therefore in a 10 to 100% molar excess, based on the epoxide groups the epoxy resins used used.
  • Reactive diluents which can be used are all of the abovementioned epoxide compounds having one epoxide group per molecule, such as aliphatic, araliphatic, cycloaliphatic, aromatic or heteroaromatic-containing compounds having one epoxide group per molecule. Examples of these are butyl, hexyl, phenyl, cresyl, butylphenyl or Nonylphenylglycidylether.
  • amines are used at least in a 10% molar excess, based on the epoxy groups of the epoxy resins used. This excess can be unlimited due to chemical considerations. But since the excess amines must be distilled off again, it is necessary for economic reasons to limit the surplus. In general, the amines are therefore used in a 10 to 100% molar excess, based on the epoxide groups of the epoxy resins used.
  • the hardener components a, b and c according to the invention can each be prepared separately and After completion in each case for the final hardener formulation are mixed together. But the curing agents according to the invention can also be prepared so that the Components a, b and c, each with their proportions of excess amine with each other are mixed and then the unreacted mono-, di- or polyamines from the Mixture be separated by distillation. If for a and b the same epoxy compound is used, this can be presented at the beginning in their entirety.
  • a further simplification of the preparation of the curing agents according to the invention can be achieved in that after the preparation of the precursor of the component a the Epoxy resins for the component b and the reactive diluents for the component c the Precursor and the sum of all mono-, di- and / or polyamines to be used added and both the final implementation and the work-up by distillation of all three Components are shared.
  • the amine-terminated curing agents according to the invention which are used as emulsion or Solution are present, optionally with additional reactive hardener components, commercial additives such.
  • additional reactive hardener components commercial additives such.
  • fillers, pigments, flow control agents, Defoamers, deaerators, etc., and others as an additive for curing agent for Epoxy resins known substances such.
  • solvents, accelerators, etc. with Epoxy compounds in particular epoxy resins having at least two epoxide groups per Molecular unit mixed in equimolar ratio of amino and epoxy groups and optionally dispersed or emulsified after addition of water with vigorous stirring, applied as emulsion or dispersion and cured.
  • the curing takes place depending on the requirements at low temperatures down to about 0 ° C within 3 to 72 hours after mixing or at elevated temperatures.
  • the curing agents thus prepared are thereafter, if their use in water emulsifiable Systems is desired, diluted with water. If necessary, you still give a lot monofunctional reactive diluents to block the reactivity of the system of primary amino groups. The amount depends on the desired Reactivity (pot life) and the desired HLB value of the curing agent. Then it will be diluted again with water, so that an emulsion and / or solution with a Water content of preferably 40% is obtained. Such emulsions are suitable in particular for the manufacture of sealants or primers and for decorative purposes Final coatings based on epoxy resin.
  • the hardener according to the invention can be further known per se known Epoxidharzhärter, in particular amine-terminated polyalkyl ethers, primary longer-chain monoamines or amine-terminated butadiene-acrylonitrile copolymers and metal complex compounds be added. These hardener mixtures are usually emulsifiable in water.
  • the curing agents according to the invention and hardener mixtures containing them can moreover, in a manner known per se with additional customary additives, accelerators, Reaction retarders are combined.
  • Such hardener mixtures can also be in water be emulsified.
  • the quantities in the examples are in each case in parts by weight.
  • the abbreviation RT means room temperature.
  • the abbreviation ⁇ q. means equivalent.
  • this precursor is under nitrogen atmosphere and with vigorous stirring over 2 h in 110 parts of triethylene tetramine and 2 h long reacted at 80 ° C (ratio of epoxide: amine: 1: 2 mol or 1:12 equivalents). Thereafter, the reaction mixture is slowly heated under vacuum to 250 ° C and not distilled off converted triethylenetetramine.
  • a product with a viscosity is obtained 25 ° C of 30000mPas, an amine equivalent of 179 g / eq. and a Gardener color number ⁇ 3.
  • 114 parts of phenyl glycidyl ether and 75 parts of p-tert-butylphenyl glycidyl ether are added successively at 90 ° C. to a mixture of 336 parts of emulsifier component from Example 1, 367.5 parts of adduct from Example 2 and 367.5 parts of adduct from Example 3.
  • 700 parts of dist. Water added.
  • the resulting curing agent has a viscosity at 25 ° C of 5000 mPas, an amine equivalent of 200 g / eq. and a Gardner color number ⁇ 3.
  • this mixture After mixing 32 parts of the curing agent with 31 parts of a reactive dilute, liquid epoxy resin (based on bisphenol A, epoxide equivalent 190 g / eq.) And 37 parts Water, this mixture has a pot life of about 120 min at room temperature. At the Applying a thin layer of this emulsion to a substrate is rapid Film formation. The end of the pot life is clearly visible through a strong increase in viscosity. The cured film shows a bright shine (175% at 20 ° measurement angle). The Pendulum hardness (after König) is 100 s after 24 h at RT and 200 s after 7 d at RT.

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Claims (15)

  1. Durcisseur pour composés de type époxyde à base de produits de réaction de polyalkylène-polyéther-monoamines et/ou -diamines et/ou -polyamines avec des di- et/ou polyépoxydes et réaction du précurseur contenant des groupes époxy, ainsi obtenu, avec une mono- et/ou di- et/ou polyamine primaire ou secondaire, caractérisé en ce que le durcisseur est constitué des composants suivants :
    a. un produit de réaction de polyalkylène-polyéther monoamines et/ou -diamines et/ou -polyamines ayant une masse moléculaire moyenne de 148 - 5 000, avec des di- et/ou polyépoxydes, éventuellement après réaction ou en mélange avec des monoépoxydes, le rapport des atomes d'hydrogène liés à l'azote, éventuellement restant après la réaction avec des monoépoxydes, qui sont aptes à la réaction avec des groupes époxy, aux groupes époxy de di- ou polyépoxydes, étant dans la plage de 1:1,4 à 1:6, réaction du précurseur contenant des groupes époxy, ainsi obtenu, avec une mono- et/ou di- et/ou polyamine primaire ou secondaire, l'amine secondaire comportant au moins deux groupes amino secondaires et l'amine utilisée ou le mélange d'amines utilisé étant utilisé(e) en un excès molaire d'au moins 10 %, par rapport aux groupes époxy du précurseur, le produit de réaction étant essentiellement exempt d'amines n'ayant pas réagi,
    b. un adduit à terminaison amino, à base d'une résine époxy et d'éthylènediamine, de diéthylènetriamine, triéthylènetétramine, tétraéthylènepentamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-, 1,3- ou 1,4-diaminobutane, 3-(2-aminoéthyl)aminopropylamine, N,N'-bis(3-aminopropyl)éthylènediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, N-aminoéthylpipérazine, N-aminopropylpipérazine, N-aminobutylpipérazine, phénylènediamines, xylylènediamines et isophoronediamine ou de mélanges de ces amines, et l'adduit étant essentiellement exempt d'amines n'ayant pas réagi,
    c. un adduit à terminaison amino, à base d'un diluant réactif contenant des groupes époxy et d'une mono- et/ou di- et/ou polyamine primaire ou secondaire, l'amine secondaire comportant au moins deux groupes amino secondaires et l'adduit étant essentiellement exempt d'amines n'ayant pas réagi.
  2. Durcisseurs selon la revendication 1, caractérisés en ce qu'ils contiennent les composants a, b et c en un rapport pondéral de 10 à 60:5 à 85:5 à 85.
  3. Durcisseurs selon les revendications 1 et 2, caractérisés en ce qu'ils ont réagi encore avec jusqu'à 50 % en moles, par rapport aux groupes amino, de diluants réactifs.
  4. Durcisseurs selon les revendications 1 à 3, caractérisés en ce que les polyalkylènepolyétheramines sont aussi bien des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde d'éthylène que des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde de propylène et/ou des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde de butylène.
  5. Durcisseurs selon les revendications 1 à 4, caractérisés en ce qu'ils sont présents sous forme d'émulsion ou de solution.
  6. Utilisation du durcisseur selon les revendications 1 à 5, en mélange avec d'autres durcisseurs usuels.
  7. Procédé pour la préparation des durcisseurs selon les revendications 1 à 6, caractérisé en ce qu'on fait réagir des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines ayant une masse moléculaire moyenne de 148 - 5 000, avec des di- et/ou polyépoxydes, éventuellement après réaction ou en mélange avec des monoépoxydes, pour obtenir un précurseur, le rapport des atomes d'hydrogène liés à l'azote, éventuellement restant après la réaction avec des monoépoxydes, qui sont aptes à la réaction avec des groupes époxy, aux groupes époxy de di- ou polyépoxydes, étant dans la plage de 1:1,4 à 1:6, on fait réagir le précurseur obtenu, contenant des groupes époxy, avec une mono- et/ou di- et/ou polyamine primaire ou secondaire, l'amine secondaire comportant au moins deux groupes amino secondaires et l'amine utilisée ou le mélange d'amines utilisé étant utilisé(e) en un excès molaire d'au moins 10 %, par rapport aux groupes époxy du précurseur, une fois la réaction terminée on sépare par distillation les mono-, di- ou polyamines n'ayant pas réagi, et on mélange les produits de réaction ainsi obtenus avec un adduit à terminaison amino, à base d'une résine époxy et d'éthylènediamine, de diéthylènetriamine, triéthylènetétramine, tétraéthylènepentamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-, 1,3- ou 1,4-diaminobutane, 3-(2-aminoéthyl)aminopropylamine, N,N'-bis(3-aminopropyl)éthylènediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, N-aminoéthylpipérazine, N-aminopropylpipérazine, N-aminobutylpipérazine, phénylènediamines, xylylènediamines et isophoronediamine ou de mélanges de ces amines et un adduit à terminaison amino, à base d'un diluant réactif et d'une mono- et/ou di- et/ou polyamine primaire ou secondaire.
  8. Procédé pour la préparation des durcisseurs selon les revendications 1 à 6, caractérisé en ce qu'on fait réagir des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines ayant une masse moléculaire moyenne de 148 - 5 000, avec des di- et/ou polyépoxydes, éventuellement après réaction ou en mélange avec des monoépoxydes, pour obtenir un précurseur, le rapport des atomes d'hydrogène liés à l'azote, éventuellement restant après la réaction avec des monoépoxydes, qui sont aptes à la réaction avec des groupes époxy, aux groupes époxy de di- ou polyépoxydes, étant dans la plage de 1:1,4 à 1:6, on fait réagir le précurseur ainsi obtenu, contenant des groupes époxy, avec une mono- et/ou di- et/ou polyamine primaire ou secondaire, l'amine secondaire comportant au moins deux groupes amino secondaires et l'amine utilisée ou le mélange d'amines utilisé étant utilisé(e) en un excès molaire d'au moins 10 %, par rapport aux groupes époxy du précurseur, une fois la réaction terminée on sépare par distillation les mono-, di- ou polyamines n'ayant pas réagi, et on mélange les produits de réaction ainsi obtenus avec un adduit à terminaison amino, à base d'une résine époxy et d'éthylènediamine, de diéthylènetriamine, triéthylènetétramine, tétraéthylènepentamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-, 1,3- ou 1,4-diaminobutane, 3-(2-aminoéthyl)aminopropylamine, N,N'-bis(3-aminopropyl)éthylènediamine, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, N-aminoéthylpipérazine, N-aminopropylpipérazine, N-aminobutylpipérazine, phénylènediamines, xylylènediamines et isophoronediamine ou de mélanges de ces amines et un adduit à terminaison amino, à base d'un diluant réactif et d'une mono- et/ou di- et/ou polyamine primaire ou secondaire, et ensuite on sépare du mélange par distillation les mono-, di- ou polyamines n'ayant pas réagi.
  9. Procédé pour la préparation des durcisseurs selon les revendications 1 à 6, caractérisé en ce qu'après la préparation du précurseur du composant a on ajoute les résines époxy pour le composant b et les diluants réactifs pour le composant c au précurseur et à l'ensemble de toutes les mono-, di- et/ou polyamines à utiliser, et on effectue conjointement aussi bien la dernière réaction que le traitement final par distillation de tous les trois composants.
  10. Procédé selon les revendications 7 à 9, caractérisé en ce que les durcisseurs sont encore mis en réaction avec jusqu'à 50 % en moles, par rapport aux groupes amino, de diluants réactifs.
  11. Procédé selon les revendications 7 à 10, caractérisé en ce qu'on utilise en tant que polyalkylènepolyétheramines aussi bien des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde d'éthylène que des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde de propylène et/ou des polyalkylènepolyéthermonoamines et/ou -diamines et/ou -polyamines à base d'oxyde de butylène.
  12. Utilisation des durcisseurs selon les revendications 1 à 6, conjointement avec un ou plusieurs composés de type époxyde et de l'eau, ainsi qu'éventuellement des charges et des additifs, comme par exemple des pigments, des antimousses ou des agents de désaération, pour la production de peintures, de compositions de revêtement et de revêtements.
  13. Utilisation des durcisseurs ou des mélanges de durcisseurs selon les revendications 1 à 6, conjointement avec un ou plusieurs composés de type époxyde et de l'eau, ainsi qu'éventuellement des charges et des additifs, comme par exemple des pigments, des antimousses ou des agents de désaération, en tant qu'additifs pour des liants hydrauliques.
  14. Utilisation des durcisseurs ou des mélanges de durcisseurs selon les revendications 1 à 6, conjointement avec un ou plusieurs composés de type époxyde ainsi qu'éventuellement des charges et des additifs, comme par exemple des pigments, des antimousses ou des agents de désaération, pour la production de matières d'étanchéité et d'adhésifs.
  15. Utilisation des durcisseurs ou des mélanges de durcisseurs selon les revendications 1 à 6, conjointement avec un ou plusieurs composés de type époxyde ainsi qu'éventuellement des charges et des additifs, comme par exemple des pigments, des antimousses ou des agents de désaération, pour la fabrication de pièces moulées flexibles, d'articles plats et de stratifiés.
EP01106910A 2000-03-23 2001-03-20 Durcisseurs de résines époxydes, procédé pour leur préparation et utilisation Expired - Lifetime EP1136509B1 (fr)

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Application Number Priority Date Filing Date Title
DK01106910T DK1136509T3 (da) 2000-03-23 2001-03-20 Epoxyhærdere, fremgangsmåde til fremstilling heraf og deres anvendelse

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10013735A DE10013735A1 (de) 2000-03-23 2000-03-23 Härter für Epoxidverbindungen, Verfahren zu ihrer Herstellung und Verwendung
DE10013735 2000-03-23

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EP1136509A1 EP1136509A1 (fr) 2001-09-26
EP1136509B1 true EP1136509B1 (fr) 2005-05-18

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US (3) US6410658B1 (fr)
EP (1) EP1136509B1 (fr)
AT (1) ATE295859T1 (fr)
DE (2) DE10013735A1 (fr)
DK (1) DK1136509T3 (fr)

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EP2365015A1 (fr) * 2010-03-10 2011-09-14 Momentive Specialty Chemicals Research Belgium Lagerbeständige härtbare Epoxyaminsysteme auf Wasserbasis
US8970217B1 (en) 2010-04-14 2015-03-03 Hypres, Inc. System and method for noise reduction in magnetic resonance imaging
CN103339166B (zh) * 2011-01-28 2016-01-20 陶氏环球技术有限责任公司 环氧加合物硬化剂
JP2015512467A (ja) * 2012-04-09 2015-04-27 ダウ グローバル テクノロジーズ エルエルシー 常温硬化性エポキシ系用の硬化剤
US20160009853A1 (en) * 2013-03-01 2016-01-14 Sika Technology Ag Composition and method of making water borne epoxy hardener for use in two-component epoxy self levelling compounds with long pot life, fast cure and low shrinkage characteristics
MX2015012288A (es) 2013-03-15 2015-12-16 Blue Cube Ip Llc Endurecedores para sistemas epoxi de vulcanizacion en frio.
US20160053108A1 (en) * 2013-05-17 2016-02-25 Blue Cube Ip Llc Hardeners for cold-curing epoxy systems
CN104151528B (zh) * 2014-08-19 2016-08-24 湖南神力胶业集团有限公司 一种环氧非活性稀释剂及其合成方法
EP3253842A1 (fr) * 2015-02-06 2017-12-13 tesa SE Matière adhésive à indice de jaunissement réduit
TW201641531A (zh) 2015-04-30 2016-12-01 藍色立方體有限責任公司 硬化劑組成物
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CN109503849B (zh) * 2018-12-04 2021-04-27 中科院广州化学有限公司南雄材料生产基地 一种反应型环氧树脂乳化增稠剂及其制备方法与应用
WO2020234066A1 (fr) * 2019-05-23 2020-11-26 Basf Coatings Gmbh Dispersion de résine aqueuse et composition de revêtement aqueuse contenant la dispersion de résine
AU2020280668A1 (en) * 2019-05-23 2021-12-16 Basf Coatings Gmbh Aqueous resin dispersion and aqueous coating composition containing said resin dispersion
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CN109082200B (zh) * 2018-07-09 2020-11-03 中国石油天然气集团公司 一种无溶剂环氧防腐蚀涂料及其制备方法

Also Published As

Publication number Publication date
US20020072576A1 (en) 2002-06-13
DE10013735A1 (de) 2001-10-11
US6646065B2 (en) 2003-11-11
EP1136509A1 (fr) 2001-09-26
ATE295859T1 (de) 2005-06-15
US6653412B2 (en) 2003-11-25
US6410658B1 (en) 2002-06-25
US20020072575A1 (en) 2002-06-13
DK1136509T3 (da) 2005-06-20
DE50106240D1 (de) 2005-06-23

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